Process for brightening foodstuffs containing carbohydrates



Patented July 21, 1953 UNITED STATES PATENT OEFICE PRGGESS F0512BRIGHTENING FOODSTUFFS v V CONTAINING CARBOHYDRATES w Hans-Heini-LZweifeL-and Franz Ackermann; Binningen Switzerland, assignorsvto CibaLinrited, Basel, Switzerland, a Swiss firm Q No Drawing. ApplicationNovembehzfig I949} See rial No. 129,872. In 1948;-

' "zz'olaims. "(mes-14st This invention relates-to the enhancement ofthe white appearance ofcarbohydrate containing foodstuifs, such as Watersoluble saccl'i'arides and flours by incorporating irr'tllemia' quantity1 which is nontoxic to man of a compound which when dissolved or whenapplied to a substratum:

shows a blue to violet-fluorescence in ultraviolet light.

If e. g. wheat flour treated in the indicated manner is used to makebaker's ware, such as bread, the appearance of the latter is muchbrighter than that of similar wares made from: untreated flour.

Among the carbohydrate-containing fondstufis whose white appearance iscapable of improvement according to the present inventiorr" may bementioned the following:

Water soluble saccharides, e. g. monosaccha rides, such as pentoses andhexoses; e. g. l-arabinose, d-glucose, d-galactose, d-fructose; alsosugar-like polysaccharides, such as cane sugar;

swit'zbrland ecembeti 1S,

wherein R' and zBi: stand for hydrogen or a substituted or unsubstitutedalkyl or aralkyl radical and Me for a cation. Compounds of this gn eralformula are easilypbtainable from the C01.- l-responding, aminocoumarinsof the formula I wherein. R1 and' R2 the aboyerindicated si nificance;by treatment with aldehyde-bismfite compounds, particularly with sodiumformaldehyde bisulfite.

or milk sugar; furthermore cereal flours, e. g: Y

wheat rye, barley, maize rice flours, also potato flour andflounfromiothen plant products As compounds, which. when, dissolved; or when"applied to, a substratum. show a-. blue to. violet fluorescence; inultraviolet, lightandwhichwhem used; in; small. quantity are none-toxicto human.

beings, there maybe mentioned the following jhy way of example:.

(A) Blue to violet. fluorescent compounds of the coumarinr series,particularly. those which naots'wzeraeng 5 (B) Blue to violetfluorescent imidazoles, thiazoles and oxazoles, for example, thecompounds of the formulae (0) Blue to violet fluorescent salts ofhydroxy or amino-naphthalene sulfonic-acids, e. g. of 2-amino-naphthalenei;disulfoni'c'acid-(6,8) or of 2- 5ovhydroxy-naphthalene-disulfonio acid-(2,6).

(D) Blue to violet fluorescent aromatic hydroxy carboxylic acids orsalts thereof, e. g. salts of salicylic acid or of carboxylic acids ofthe for- (G) Blue to violet fluorescent furan derivatives, mula such as2,8,4,5-tetraphenyl furan or the compound of the formula NH-o O-NH- 5 fi/C 0 1 9? .QMO K (obtainable from benzoin and hydroquinone).

OOH I *(H) Blue to violet fluorescent compounds of and 1 the carbazolseries.

(I) Esters, i. e. lower alkyl esters, such as OH methyl, ethyl, propylesters or araliphatic esters,

' j 'suchasbenzyl esters of dihydrocollidine dicar- O GOOH I boxylicacid of the formula (E) Blue to violet fluorescent compounds of thediphenyl, dibenzyl, or stilbene, series, erg. salts of sulfonic acidswith the atom grouping O OO0H Examples thereof are salts of sulfonicacids of the wherein R stands for an alkyl, aryl-, aralkyl-,

formula or a heterocyclic radical.

03H AOsH run-( 3 e-NH ar on-Own e-mn i N I v N N 03H SOaH r i NH NHThere may, however, also be employed the unsulfonated compounds having.the aforemenamino groups, made from arylamines and arotioned atomgroupings, and those with the atom matic carboxylic acids, as well asderivative of grouping 7 these amides whose amino group is substitutedby alkyl or aralkyl radicals. An example of this class of compounds isthe compound of the for- An example of the compound of the diphenylseries comprised within the present invention is n p ct c ng th presentprocess a q lty th following; of the fluorescent compounds mentioned,which I SO3N8 OaNa (F) Blue to Violet fluorescent compounds of is sosmall as to be non-toxic to man, say, 0.001 the4,5-diphenyl-imidazolone-(2)-series, such as to 05 per cent by Weight,may be mixed with the compound- Qf the formula" the foodstufiscontaining carbohydrates, by grind- 7 NH ing the dry ingredients to bmixed. Alterna- O tively, the aforementioned fluorescent substances 0:0of their production. They may, for instance, be admixed to the flour tobe brightened While the latter is being ground. The. fluorescent submaybe mixed with such foodstuffs in the course stances to be used inaccordance with this in- (J) Blue to violet fluorescent amides withbasic momma;

ventiom cam 8159?; tom. OtISOhIrtionslwithr subsequent geliminatiom offthe: solventtthe: case? of? carbohydrates; obtained; from;aqueous.solutionszsucmasrissthwcaseiwithisugari. those? of the;aforementioned: fluorescent: come; pounds which arewaterrsolubleemawbeaaddeditw v suclissolutionszp Example; 1:?

and round-E this" marinerthe -white appearanceofi'theflour isconsid'erabli enhanced By usi'ngj irrlieu 'of 4-methly etliylamihmeoumarin; -methy I---'6 methyl 'l ethylwmino cou marin; oi the coumarih oftl-ie"formuladeem -(momma amino-coumarirr with formaldehyde: sodium 'bi.

sulfite; obtainediaccordingto Example" 2 of U2. S: patent'anplic'ationSeriaLNo; 7523277} fil'ed June 6; I947i' flour-with similargropertiesris obtainedi Wheat flourcan be replaced by maize or" riceflour.

1000' parts of" white} wheat. flour: andylr. part. oi. sodiumefi-umbelliferonei acetate are; mixed2 to getherrandgroundl In this manner.aconsiderabletbrightening of; the flour is efi'ected.

In lieu of sodium-,8-methyl-umbelliferone acetate there may beuseds'other coumarins with a 7-positioned hydroxy group such. as4.-methy1-7-' hydroXy-coumari'n or: 4-methyl 5E7-dihydroxycoumarin, or aglucoside thereof; such as esculin. Mternatively, another of thebrightening agents mentioned in the introductory part of thespecification. may be. used,, f on examnle Z ta-amino fienyma-mtnyL-benahi w;

' Examble a I Glucose is mixed andground with 0.05 per centi of itsweight of-4methyl-7-ethylaminocoumarin,

and in this way its appearance is considerably brightened.

Example 5 At any'stage of the preparation from white wheat flourof-adough for bakers-ware, there is added0102 per centzby; weight of the,sodium salt of the sulfonated 3-benzyl-4- methyl-7-ethylaminoz-coumarin, dissolved in; water. This salt is obtainableaccording to U. S. patent application; Serial :No; -'Z52,2717, filedJuneifi, I947 The resultant" doughzhasa. brighter appearance than asimilar dough madewithout the addition in question.

. A similar brightening: efi'ect results from-the use of i -methyl ldimethylaminomoumarin; dis' 1 solved in ethyl al'cohol} in lieu"ofthesodiunrsalt of thesulfonated lif-benzyl-4-methyl l ethyl amino coumarin.T

7 Example 6 parts of refined-cane or beet sugar are mixed with0.00.1..partfof 'emethyle'l -dimethylamino-coumarin and ground... Theresultant sugar has a whiter appearance than sugar ground without thisaddition. In lieu of the aforementioned coumarin, other coumarins may beused which carry as 7-positioned substituent an amin alkylaminaorhydroxylzgroups The." brightening j ofv the sugar: may alternatively beeffected by adding the brightening agenttmene tioned.- tor a: refinedsugar solution; instead:v of to the finished; sugar; @n -evaporationa ofthe solue tion there is also obtained a sugar presenting a brighterappearance than sugar not so treated.

E'zrample 7- 1000 parts of whitewheat flour and 1 part of4,5-diphenyl-imidazolonee('2) of the formula are mixedtogethen and.ground. In; this; manner. a considerable-brightening. of. the flouriseffected. Instead of thacompoundof the above-formula...

' substitution. productsthereof may be used, e.

itssN -alkylatedor N-arylated. derivatives, suchas. its..N.-methyl-,N'-ethyl.-,. or N.-phenyl derivative;

Example" 8 100,- parts: of. whitew wheat fiour are thoroughly mixed:with. 0.2: part of; the.- compounds. of: the.- formula.

which; maybe prepared according. to-the data:

given. in; Qhemischesi. Zentralbla-tt. 1930, I, page this;- additiflhzthan; without.

1292.: The, flour. has: a, whiter; appearance-.- with;

the same quantity of the compound of the formula or of the formula ICOOH COOH At any stage of the preparation from white wheat flour of adough for bakers ware, there is added 0.2 per cent. by weight of thediethyl ester of dihydrocollidine dicarboxylic acid of the formula C-CHa021150 o o-o CHrr-C A similar brightening effect results from the use ofthe furan derivative of the formula What is claimed is:

1. A foodstuff composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-soluble saccharides and flours and 0.001 to 0.5 per cent. byweight of an odorless substance which is free from groups impartingdyestuff characteristics to thecompound and when dissolved shows a blueto violet fluorescence in ultraviolet light, which is non-toxic to manwhen applied in the concentrations indicated above, and which isselected from the group consisting of'compounds of the coumarin seriessubstituted in the 7-position by a basic amino group, compounds of thecoumarin series substituted in the i-position by a hydroxy group,glucosides of compounds of the coumarin series substituted in the7-position by a hydroxy group, esters of dihydrocollidine dicarboxylicacid, and alkali metal salts of dibenzofurane-3-hydroxy-4-carboxylicacid, said foodstuff composition appearing to be whiter in color thanthe" carbohydrate per se.

2. A foodstuff composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-soluble saccharides and flours and 0.001 to 0.5 per cent by weightof an odorless compound of the coumarin series substituted in the'7-position by a basic amino group, which compound is free from groupsimparting dyestuff characteristics to the compound and when dissolvedshows a blue to violet fluorescence in ultraviolet light and which isnon-toxic to man whenapplied in the concentrations indicated above,saidfoodstuff composition-appearing to be whiter in color than thecarbohydrate per se.

3. A foodstuff composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-soluble saccharides and flours and 0.001 to 0.5 per cent. byweight of an odorless compound of the coumarin series substitutedin thee-position by a methyl group and=in the 7-position by abasic aminogroup, which compound is free from groups imparting dyestuffcharacteristics to the compound and when dissolved shows a blue toviolet fluorescence in ultra-violet light and which is non-toxic to manwhen applied in the concentrations indicated above,-'said foodstuffcomposition appearing to be Whiter in color than the carbohydrate perse.

4. A foodstuif composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-solu- "ble saccharides and flours .and 0.001 to 0.5 per cent byweight of an odorless compound of the coumarin series substituted in thel-position by a methyl group andin the '7-position bya monoalkylatedamino group, whichcompound is-free from groups imparting dyestuffcharacteristics to the compound and when" dissolved shows a blue toviolet fluorescence in ultraviolet light and which is non-toxic to manwhen applied in the concentrations indicated above, said foodstuffcomposition appearing to be whiter in color than the carbohydrate perse. 7

5. A foodstuff composition of enhanced whitenesswhich consistsessentially .of-a carbohydrate selected fromthe groupconsisting ofwater-soluble saccharides'and ,fic urs and 0.001 to per cent. by weightof 4-methyl-7-ethy1aminocoumarin, said foodstuff composition appearingto be whiter in'color than the carbohydrate perse.

6. A foodstuff composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-soluble saccharides and flours and 0.001 to 0.5 per cent. byweight of 4-methyl 7-dimethylaminocoumarin, said foodstuffcompositionappearing to be whiter in colorthan'the carbohydrate per nesswhich consists essentially ofa carbohydrate selected from the groupconsisting of water-soluble saccharides'and flours and 0.001 to 0.5 percent. by Weight of -methyl-7-hydroxy-coumarin, said foodstuffcomposition appearing to be whiter in color than the carbohydrate perse;

8. A foodstuff composition of enhanced whiteness which consistsessentially of a carbohydrate selected from the group consisting ofwater-soluble saccharides and'flours and 0.001 to 0.5 per cent. byweight of diethyl ester of dihydrocollidine dicarboxylic acid of theformula /C H\. CrH5OOCC CCOOC2H5 CH -C O-CH f 11 said foodstuffcomposition appearing to be whiter in color than the carbohydrate perse.

7. A foodstuff composition of enhanced white- 7 plied in theconcentrations indicated above, and

hydrate selected from the group consisting of eyeing-est r i -e -il 9'.A foodstuff co mposition oienhanced whiteness hich consists essentiallyo whitewheat weightaifi an odorless cornfiiafi-h s'ries substituted inthe to 0.5 per c pofiiiiilidfith tion by a "mono-alkylated amino group,which con'ipo'u'hd is fre frerti griip's ilripalrtiiig dyestuffcharatceri stics togdihe icomppund iahd 'when disflour and 0.001-0.5percent. by weight of 4-methy1-7 dimethylamino-coumarin, said food- 10stufif'composition appearing to be whiter in color than the wheat flourper se.

11. A foodstuif composition of enhanced whiteper se.

apor than the carbohydrate ness which consists essentially of beet sugarand 16. A proces f0 enhancing e ess of a 0.001-0.5 per cent. by weightof 4-methyl-7-difoodstuff which consists essentially of acarbomethylamino-coumarin, said foodstuif composiy Se ed from t oupConsisting o tion appearing to be whiter in color than the beetWater-Soluble s c s d flou w c sugar per comprises intimately mixing thefoodstuff with 12. A process for enhancing the whiteness of 0-001 t0 p reeIitby Weight of y a foodstuff which consists essentially of a carbo-20, y inoumarin. wh r by th r su ta t composition appears to be whiterin color than hydrate selected from the group consistingof thecarbohydrate per se.

water-soluble saccharides and flours, which comg V V prises intimately,mixing the foodstuff with 0.001 17- A pr cess for enh in h whiteness ofa to 0.5 per cent. by weight of an odorless substance foodstuff ich cosist es e lly of a carbowhich is free from groups imparting dyestufihydrate selected from the group co s g of characteristics to thecompound and when djswater-soluble saccharides and flours, which solvedshows a blue to violet fluorescence in ultraeomprises intimately mixingt e foodstuff With violet light, which is non-toxic to man when ap- 0001to p centby weight of y dimethylamino-coumarin, whereby the resultantwhich is selected from the group consisting of comp i pp ars o be whiterin color the compounds of the coumarin series substituted inthe'carbohyd a e p r e. the 7-position by a basic amino group, compounds18. A pr cess for nh ncin the whiteness of a of the coumarin seriessubstituted in the 7-posiv foodstuff which consists essentially ofacarbotion byahydroxy group, glucosides of compounds a e l d m he group cns of of the coumarin series substituted in the 7- os'i- 35.Water-soluble saccharides and flours, which comti by a hydroxy u estersof d np prises intimately mixing the foodstufi with 0.001 dinedicarboxylic acid, and alkali metal salts of to p cent-by Weight of -mey ydibenzo-furane-B hydroxy 4 carboxylic acid, d xyou ri w r y the su tmp siwhereby the resultant composition appears to be tleh ppears to bewhiter in color than the carbowhiter in color than the carbohydrate perse. 40 hydr t p Se- I 13. A process for enhancing the whiteness of a A pss for enhancing e whiteness of foodstufi which consists essentially ofa carbofOOdStllfi Which co essentially of a Cerbehydrate selected fromthe group consisting of y r selected f m the gr p s in f water-solublesaccharides and flours, which comat r-solub e cc i d flours. whichprises intimately mixing the foodstufi with 0.001 prises intimatelymixing t e foodstuff with 0.001 to 0.5 percent; by weight of an odorlesscomto p r e t. by Weight of diethyl s er of pound of the coumarin seriessubstituted in the' 'l- 'dihydreeellidine dicer-hexylie c d of the omula position by a basic amino group, which compound is free from groupsimparting dyestuff CH3 characteristics to the compound and when dis- ,50I solved shows a blue to violet fluorescence in ultrav violet light andwhich is non-toxic to manwhen G CCOOCZHB applied in the concentrationsindicated above, OH;;-@ whereby the resultant composition appears to beI whiter in color than the carbohydrate per se. 7

14. A process for enhancing the whiteness of a, V foodstuif whichconsists essentially of a carbo I i hydrate selected from the groupconsisting of whereby t resultant Composition pp s to water-solublesaccharides and flours, which combe whiter in color than the c rbohy r pr prises intimately mixing the foodstuff with 0.001 A pr ss f enhancingth whiteness of t 0.5 per cent, by weight of an d rl omwhite wheat flourwhich comprises intimately pound of the coumarin series substituted inthe 4- i i the ur With 0 per cent. by position by amethyl group and inthe 7-position weight of 4 methyl 7 e ylamino coumarin, by a basic aminogroup, which compound is free whereby the resultant composition appearsto be from groups imparting dyestuffs characteristics Whiter in colorthan the flour per se. to the compound and when dissolved shows a blue21. A p oce s f r nha the whit n ss of to violet fluorescence inultraviolet light andv v White wheat flour which c mpri s int ly dwhichis non-toxic to man when applied in the mixing flour With 01101-05 pcent by concentrations indicated above, whereby the re- Weight of4-methyl-7-dimethylamino-coumarin, sultant composition appears to bewhiter in color 7 whereby the resultant Comp sition appears to be th thcarbohydrate per whiter in color than the flour per se.

15. A process for enhancing the whiteness of a. v 22. A process forenhancing the whiteness of foodstuff which consists essentially of acarbobeet sugar which comprises intimately admixing the beet sugar with0.001-0.5 per cent. by weight water-soluble saccharidesgand flours,which com- 7 0f 4-methyl-7-dime hy1amin0- 0umarin,whereprisesintimatelynnixingrthemoo'dstufifwithiihnftl4-positibhflziyib, hetliyl'igfoup and in the 7-posi-- 1 1 by theresultant compositidn'appears tobe whiter color than the beet sugar perSe. v

HANS HEINI ZWEIFEL. FRANZ ACKERMANN.

References Cited in theme of this patent UNITED STATES PATENTS NumberName Date 576,860 Lanaux Feb.. 9, '1897 2,146,958 Kotera Feb. 14, 1939OTHER REFERENCES Rehwaidz Starch Making, pub, by Scott, Greenwood andSon, London, 1926, pp. 200-201.

Fairrie, Sugar, pub. by Fairrie and Co. Ltd., Liverpool, 1925, page 101.

Chemical Abstracts 42: 7044 (a), Joseph Lyman Switzer et 2.1.. Canada447, 751, April 13, 1948.

1. A FOODSTUFF COMPOSITION OF ENHANCED WHITENESS WHICH CONSISTSESSENTIALLY OF A CARBOHYDRATE SELECTED FROM THE GROUP CONSISTING OFWATER-SOLULE SACCHARIDES AND FLOURS AND 0.001 TO 0.5 PER CENT. BY WEIGHTOF AN ODORLESS SUBSTANCE WHICH IS FREE FROM GROUPS IMPARTING DYESTUFFCHARACTERISTICS TO THE COMPOUND AND WHEN DISSOLVED SHOWS A BLUE TOVIOLET FLUORESCENCE IN ULTRAVIOLET LIGHT, WHICH IS NON-TOXIC TO MAN WHENAPPLIED IN THE CONCENTRATIONS INDICATED ABOVE, AND WHICH IS SELECTEDFROM THE GROUP CONSISTING OF COMPOUNDS OF THE COUMARIN SERIESSUBSTITUTED IN THE 7-POSITION BY A BASIC AMINO GROUP, COMPOUNDS OF THECOURMARIN SERIES SUBSTITUTED IN THE 7-POSITION BY A HYDROXY GROUP,ESTERS OF DIHYDROCOLLIDINE DICOURMARIN SERIES SUBSTITUTED IN THE7-POSITION BY A HYDROXY GROUP, ESTERS OF DIHYDROCOLLIDINE DICARBOXYLICACID, AND ALKALI METAL SALTS OF DIBENZOFURANE-3-HYDROXY-4-CARBOXYLICACID, SAID FOODSTUFF COMPOSITION APPEARING TO BE WHITER IN COLOR THANTHE CARBOXYHDRATE PER SE.